Monomer with anti-microbial character, polymer using the same, and manufacturing method thereof

ABSTRACT

The present invention relates to a monomer with anti-microbial characteristics, a polymeric compound with anti-microbial characteristics using the same, and manufacturing methods thereof, and more particularly, to an antimicrobial monomer comprising a saturated hydrocarbon having a polymerizable functional group within its structure. Also, the present invention provides a polymeric compound using the above antimicrobial monomer, a manufacturing method thereof, and a polymeric resin composition. The compounds according to the present invention have durable antimicrobial activity and high heat resistance, they do not give rise to toxicity when added to conventional resins by not eluting the antimicrobial compounds, and they do not have an effect on the properties of molded products.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to a monomer with anti-microbialcharacteristics, a polymeric compound with anti-microbialcharacteristics using the same, and manufacturing methods thereof, andmore particularly, to an antimicrobial monomer that has durableantimicrobial activity and high heat resistance, does not give rise totoxicity when added to conventional polymeric resins and petrochemicalproducts by not eluting antimicrobial compounds, and does not have aneffect on the properties of molded products, an antimicrobial polymerusing the same, and manufacturing methods thereof.

(b) Description of the Related Art

Recently, in line with great concerns about environmental hygiene andhigh-grade life style, the production of and demand for productsconferring antimicrobial characteristics to petrochemical materials foruse in industrial supplies such as food wrappers, containers forstorage, toothbrushes, cutting boards, stationery, washing tubs, waterpurifiers, shampoos, soaps, cosmetics and wrappers, and medicalsupplies, are increasing.

In the case of organic antimicrobial substances used in these products(ex: quaternary ammonium salts, triazines, benzimidazole, triclosan,chlorohexidine, thiazoles, etc.), in order to confer antimicrobialability to polymeric substances, the antimicrobial substances are simplyadded to the polymeric substances when manufacturing antimicrobialmaterials. However, it has been reported that the antimicrobialmaterials have technical limits in respect to the inherent toxicity ofantimicrobial substances, the elution of antimicrobial substances, thereduction of antimicrobial ability due to the elution, and so on.Especially in the case of injecting or extruding plastics, antimicrobialsubstances may be decomposed by high heat, and they may also induce ayellowing phenomenon (low heat resistance).

In order to overcome the limits as described above, a simple mixingmethod with inorganic ceramic anti-microbial complexes is widely used.However, such a method also has the problem that the antimicrobialactivities are chemically decreased when they come into contact withmoisture (JAPAN NEWS Feb. 11 (Wed.), 1998, Monthly Ceramics No. 2,1998). In addition, research on binding antimicrobial substances topolymers is in progress. Pittman disclosed a method of co-polymerizingpentachlorophenylacrylates and acrylic monomers in 1981 (Pittman et al.,J. Appl. Polym. Sci., 1981, 26, 2403), and Korean Patent Application No.97-62102 disclosed a method of directly mixing antimicrobial agents withfibers, leathers, or plastics, and molding and processing them using thechemical reaction between the antimicrobial agents and polymers.However, such methods still did not solve the problems of qualitydeterioration of products since the antimicrobial ability was lost dueto heat degradation during manufacturing processes, yellowing occurred,and the mechanical properties of the molded articles deteriorated ordispersion in the formed articles was poor. Moreover, U.S. Pat. No.5,798,115 disclosed a method of using quinolinecarboxylic compounds as aback bone, but it also did not solve the problems owing to the elutionof antimicrobial substances.

SUMMARY OF THE INVENTION

Therefore, the present invention has been made to solve the problems ofthe prior arts as described, and it is an object of the invention toprovide an antimicrobial monomer having durable antimicrobial activitywith excellent heat resistance and compatibility.

It is another object of the present invention to provide a method ofmanufacturing a novel antimicrobial monomer compound.

It is a still another object of the invention to provide anantimicrobial polymeric compound having durable antimicrobial activitywith excellent heat resistance and compatibility using the aboveantimicrobial monomer compound and a manufacturing method thereof.

It is still another object of the invention is to provide a polymericresin composition comprising the above antimicrobial monomer or theantimicrobial polymeric compound using it.

It is still another object of the invention is to provide a method ofapplying the antimicrobial monomer compound as a coating agent for UVlight by simply adding it to petrochemical products and chemicallyirradiating it with UV light (by virtue of the presence of reactivegroups).

In order to achieve the aforementioned objects, the present inventionprovides an antimicrobial monomer compound represented by the followingformula 1:

-   -   wherein    -   R is a saturated or unsaturated C₁ to C₁₅₀ hydrocarbon        comprising a polymerizable functional group and a light-curable        reactive functional group;    -   R₁ and R₂ are each independently or simultaneously hydrogen, a        halogen atom, an amine, or a C₁˜C₂₀ alkyl group;    -   R₃ and R₄ are each independently or simultaneously hydrogen, a        hydroxy group, a C₁˜C₂₀ alkoxide, a halogen atom, or a C₁˜C₂₀        alkyl group;    -   R₅ is hydrogen, a C₁˜C₂₀ alkyl, a cyclopropyl, or an aromatic        C₁˜C₂₀ hydrocarbon;    -   R₆ is hydrogen, sodium, potassium, or a C₁˜C₁₅₀ alkyl group that        comprises or does not comprise a polymerizable functional group;    -   R₈, R₉, and R₁₀ are each independently or simultaneously carbon        or nitrogen; and

R₁₁ is hydrogen, an amine (1°, 2°, 3°), a halogen atom, or a C₁˜C₂₀alkyl group.

Also, the invention provides a method of manufacturing the antimicrobialmonomer compound of said formula 1 comprising the step of reacting acompound of the following formula 2:

-   -   wherein R₁˜R₆ and R₈˜R₁₁ are as defined in formula 1 above; with        a compound of the following formula 3:        R-Z  [Formula 3]    -   wherein R is as defined in formula 1 above and Z is a halogen        atom, or a leaving group comprising a tosyl or a mesyl;    -   in the presence of a solvent with or without a base.

Also, the invention provides a method of manufacturing the antimicrobialmonomer compound of said formula 1 comprising the epoxy ring-openingreaction of a compound of the following formula 2:

-   -   wherein R₁˜R₆ and R₈˜R₁₁, are as defined in formula 1 above;        with a compound of the following formula 3a:    -   wherein R₇ is a saturated or unsaturated C₁ to C₁₄₈ hydrocarbon        comprising a polymerizable functional group;    -   in the presence of a solvent with or without a base.

Also, the invention provides an antimicrobial homopolymer having anaverage molecular weight of 10,000˜1,000,000 represented by thefollowing formula 4:

-   -   wherein R, R₁˜R₆, and R₈˜R₁₁ are as defined in formula 1 above,        and    -   X is an integer greater than zero satisfying the above molecular        weight.

Also, the invention provides a method of manufacturing the antimicrobialhomopolymer of formula 4 comprising the step of radically polymerizingthe antimicrobial monomer compound of formula 1 as defined above in thepresence of an organic solvent and a catalyst (initiator).

Also, the invention provides an antimicrobial copolymer having anaverage molecular weight of 10,000˜1,000,000 represented by thefollowing formula 5:

-   -   wherein    -   R₁, R₁˜R₆, and R₈˜R₁₁ are as defined in formula 1 above,    -   m and n are each an integer greater than zero satisfying the        above molecular weight, and    -   Y is a monomer group capable of reacting a radically        polymerizable functional group.

Also, the invention provides a method of manufacturing the antimicrobialcopolymer of formula 5, comprising the step of radically copolymerizingthe antimicrobial monomer compound of formula 1 with monomer Y having apolymerizable functional group in the presence of an organic solvent anda catalyst (initiator).

Also, the invention provides a method of manufacturing an antimicrobialpolymeric compound comprising the steps of binding the antimicrobialmonomer of formula 1 to a linker selected from the group consisting ofan isocyanate class, a haloacylhalogenade and a compound containing anacid anhydride in the presence of an organic solvent, and then reactingit with a polyol.

Also, the invention provides an antimicrobial polymeric compoundmanufactured by the process as described above.

It is preferred that the above antimicrobial polymeric compound isselected from the group consisting of compounds represented by thefollowing formula 6 to 9:

-   -   (in the formula 6 to 9, R′ is a group represented by the        following formula b:    -   wherein R₁ R₁˜R₆, and R₈˜R₁₁ are as defined in formula 1 above.)

Also, the invention provides an antimicrobial acrylic copolymer havingan average molecular weight of 10,000˜1,000,000 represented by thefollowing formula 10:

-   -   wherein    -   R₁₂ and R₁₃ are each independently or simultaneously hydrogen or        a methyl group, R₁₄ is a C₁˜C₁₈ alkyl group comprising one or        more selected from the group consisting of ester, carbonyl,        amide, amine, cycloalkyl, ether, hydroxy, carboxylic acid,        C₂˜C₁₀ hetero ring containing N or O, sulfonyl, silane, lactone,        and aldehyde groups,    -   m and n are each an integer more than zero satisfying the above        molecular weight, and    -   X is a compound of the following formula 2a:

Also, the invention provides a method of manufacturing an antimicrobialacrylic copolymer of formula 10 comprising the step of radicallypolymerizing a compound of the following formula 11:

-   -   wherein R₁₂ is hydrogen or a methyl group, and    -   X is the compound of formula 2a as defined above;        with a compound of the following formula 12:    -   wherein R₁₃ is hydrogen or a methyl group, and R₁₄ is a C₁˜C₁₈        alkyl group comprising one or more selected from the group        consisting of ester, carbonyl, amide, amine, cycloalkyl, ether,        hydroxy, carboxylic acid, C₂˜C₁₀ hetero ring containing N or O,        sulfonyl, silane, lactone, and aldehyde groups.

Also, the invention provides an antimicrobial polymeric resincomposition in which

-   -   a) a polymeric resin, and    -   b) one or more antimicrobial compounds selected from the group        consisting of the antimicrobial monomer compound of formula 1,        the antimicrobial homopolymer compound of formula 4, the        antimicrobial copolymer compound of formula 5, the antimicrobial        polymeric compounds of formula 6 to 9, and the acrylic copolymer        of formula 10 are uniformly mixed.

Also, the invention provides a light-curable resin compositioncomprising an acrylic light-curable oligomer, a property-fortifiedmonomer, a light initiator, and an additive,

-   -   in which the light-curable resin composition comprises one or        more antimicrobial compounds selected from the group consisting        of the antimicrobial monomer compound of formula 1, the        antimicrobial homopolymer compound of formula 4, the        antimicrobial copolymer compound of formula 5, the antimicrobial        polymeric compounds of formula 6 to 9, and the acrylic copolymer        of formula 10.

Also, the invention provides a molded and processed product comprisingthe polymeric resin composition. It is preferred that the molded andprocessed products are industrial supplies, various wrappers, consumersupplies or medical supplies, and they can be applied to interiormaterials such as blinds, wall papers and floor coverings; food relatedproducts such as films for wrapping, storage containers, and cuttingboards; appliances such as humidifiers, washers, and dish washers;engineering materials such as water supply and drain pipes, andconcrete; core materials in medical fields; and products for industrialpurposes such as coatings. They are particularly useful for medicalsupplies, that is, medical devices/products for insertion into the humanbody such as catheters for medical purposes, prostheses, and productsfor repairing bones, or blood transfusion bags for medical purposes.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is hereafter described in detail.

The inventors found a novel antimicrobial monomer during the process ofresearching polymeric substances with anti-microbial characteristics,verified that polymeric compounds manufactured from the aboveantimicrobial monomer using a light-curable,homopolymerizable/copolymerizable or intermediate-binding linker solvedtoxic problems due to elution, had durable anti-microbial effects andhigh heat resistance, and had high durability when manufactured intoproducts, and thus completed the present invention.

In the present invention, R in formula 1 is preferably a saturated orunsaturated C₁˜C₂₀ hydrocarbon comprising a light-curable reactivefunctional group and a polymerizable functional group, and R₆, whichcomprises a polymerizable functional group, is preferably a C₁˜C₂₀ alkylgroup.

The above polymerizable functional group is one or more selected fromthe group consisting of carbon-carbon double bond (C═C) andcarbon-carbon triple bond (C═C), sulfonyl, halogen atom, nitro, hydroxy,thionyl (—SH), amine (1°, 2°, 3°), amide, amine, carbamate, oxime,carbonyl, carboxy, epoxy, acryl, ester, phenyl, vinyl, and nitrilegroups.

Examples of the antimicrobial monomer compound of formula 1 of thepresent invention include1-ethyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3-methyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3,5-dimethyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,1-cyclopropyl-6-fluoro-7-[4-(3-dodecafluoro-2-hydroxy-4-oxaundecyl)-3-methyl-1-ppiperazinyl]-1,4-dihydro-5-methyl-4-oxo-3-quinoline carboxylic acid,1-ethyl-6,8-difluoro-1,4-dihydro-7-{4-[2-hydroxy-3-(methoxy)phenoxypropyl]-3-methyl-1-piperazinyl}-4-oxo-3-quinoline carboxylic acid,1-ethyl-6-fluoro-1,4-dihydro-7{-4-[2-hydroxy-3-(toluene-4-sulfonyloxy)-propyl]-1-piperazinyl}-4-oxo-3-quinolinecarboxylic acid,1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid, etc.

The compound of formula 1 of the present invention can be manufacturedby two methods as shown in scheme 1 and scheme 2, below.

First, the method according to scheme 1 is as follows:

In the above scheme 1, R, R₁ to R₁₁, and Z are as defined above, and itis preferred that Z is generally a halogen atom —F, Cl, Br, or I— and aleaving group is a mesyl group (—OMs) or a tosyl group (—OTs).

In the present invention, the anti-microbial monomer of formula 1 ismanufactured by reacting the compound of formula 2 with the compound offormula 3 as shown in the above scheme 1.

The ratios of the reaction compounds can be suitably adjusted, and it ispreferred that the adding ratio of the compound of formula 3 with regardto the compound of formula 2 is 1:0.8 to 1:1.5 in terms of equivalentratio.

The reaction temperature is not limited, but it is preferably −40 to130° C. Also, to eliminate the acids that occur during the reaction, forexample hydrogen chloride, a scavenger can be further added. As thescavenger, tetramethylguanidine, diethylamine, pyrrolidine,trimethylamine, triethylamine, pyridine or piperidine, calciumhydroxide, sodium hydroxide, calcium carbonate, potassium carbonate, andso on can be used alone or in a mixture of two or more kinds, and it ispreferable to use the scavenger in an equivalent ratio of 1:1 to 1:3with regard to the compound of formula 2.

Further, according to the present invention, the anti-microbial monomercompound of formula 1 can be manufactured by an epoxide ring-openingreaction of the compound of formula 2 with the compound of formula 3a,as shown in the following scheme 2:

In the above scheme 2, R, R₁ to R₁₁, and Z are as defined above, and R₇is a saturated or unsaturated C₁ to C₁₄₈ hydrocarbon comprising apolymerizable functional group. Preferably, R₇ is a saturated orunsaturated C₁˜C₂₀ hydrocarbon comprising one or more functional groupsselected from the group consisting of sulfonyl, halogen atom, nitro,hydroxy, thionyl (—SH), amine (10°, 2°, 3°), amide, imine, carbamate,oxime, carbonyl, carboxy, epoxy, acryl, ester, phenyl, vinyl, andnitrile groups.

The ratio of the reaction compounds is not limited, but it is preferablydesirable that the equivalent ratio of the compound of formula 3a withregard to the compound of formula 2 is 1:0.8 to 1:4. Likewise, thereaction temperature is not limited, but it is preferably 35° C. to 150°C.

Both of the above reactions can be carried out in the presence of anindividual organic solvent or a mixed organic solvent of two or morekinds. The organic solvent can be selected from the group ofN,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, xylene,tetrahydrofuran, benzene, toluene, acetonitrile, dichloromethane,ethylacetate, butylacetate, 1,4-dioxane, and chloroform, but is notnecessarily limited thereto.

The compound of formula 2 used in the above schemes 1 and 2 can beprepared according to the known methods, or it may be commerciallyavailable. Examples of the compound of formula 2 include1-cyclopropyl-6-fluoro-1,4-dihydro-5-methyl-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid,1-ethyl-6,8-difluoro-1,4-dihydro-7-(3-methyl-1-piperazinyl)-4-oxo-quinolinecarboxylic acid,8-ethyl-5,8-dihydro-2-(1-piperazinyl)-5-oxo-pyrido[2,3-d]pyrimidine-6-carboxylicacid,(cis)-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7-(3,5-dimethyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid,1-(2,4-difluorophenyl)-6-fluoro-1,4-dihydro-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid,1-ethyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid,1-cyclopropyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid, and salts thereof.

The compound of formula 3 and the compound of formula 3a can be preparedby the known methods. The compound of formula 3 is a halogen compoundincluding acryloylchloride, methacryloylchloride, vinylchloride, orvinylbenzylchloride. Also, the compound of formula 3a is an epoxidederivative compound, and for example one or more compounds selected fromthe group of consisting of glyceroldiglycidylether,2-methylacrylicacidoxyranylmethylester, glycidylnonylphenylether,glycidyldodecafluoroheptylether, glycidyl-4-methoxyphenylether,2-methylacrylicacidoxyranylester, 2,3-epoxypropylmetharcrylate,4-chlorophenylglycidylether, 1-chloro-2,3-epoxypropane,glycidylmethacrylate, glycidol, acrylicacidoxyranylmethylester,2-aryloxymethyloxyrane, 2-pent-4-enyloxyrane, 2-vinyloxyrane,hexadecafluorononyloxymethyloxyrane, dodecafluoroheptyloxymethyloxyrane,octafluoropentyloxymethyloxyrane, 2-(4-nonylphenoxymethyl)oxyrane,4-nitrobonzoicacidoxyranylmethylester,nitrobenzenesulfonicacidoxyranylmethylester,toluene4-sulfonicacidoxyranylmethylester, trityloxylmethyloxyrane,1,3-bisoxyranylmethyoxypropane-2-olglycerolpropoxylatetriglycidylester,epichlorohydrine, and glycidoxypropyltrimethoxysilane can be used.

Also, the present invention provides an anti-microbial polymericcompound represented by a compound of the following formula 4:

-   -   wherein R, R₁ to R₆, and R₈ to R₁₁ defined above;    -   or a compound of the following formula 5:    -   wherein R, R₁ to R₆, and R₈ to R₁₁, m, n, and Y are each as        defined above using the anti-microbial monomer of formula 1. In        the above formula 5, Y is preferably selected from the group        consisting of a vinyl alcohol, acrylonitrile, butadiene, acrylic        acid, styrene, acrylimide, methylmathacrylic acid,        vinylchloride, vinylfluoride, an isocyanate class compound,        vinyl acetate, and derivatives thereof.

The compound of formula 4 is a homo-polymer compound manufactured fromthe radical polymerization of a polymerizable functional group using thecompound of formula 1 as a monomer. It is preferred that the compound offormula 4 has an average molecular weight of 10,000 to 1,000,000.

Also, the compound of formula 5 is an antimicrobial copolymermanufactured by the radical co-polymerization of the antimicrobialmonomer compound of formula 1 with monomer Y having a polymerizablefunctional group. It is preferred that the compound of formula 5 has anaverage molecular weight of 10,000 to 1,000,000.

The manufacture of the compound of formula 4 and the compound of formula5 of the present invention follows the following scheme 3:

The radical reaction to manufacture the compounds of formula 4 and 5 inthe above scheme 3 is carried out by the addition of a conventionalinitiator.

As the initiator, any known initiators can be used, and for example, itis preferred that they are selected from the group consisting ofazo-bis-iso-butylnitrile (AIBN), azobisdimethylbeleronitrile,benzoylperoxide, t-butylhydroperoxide, t-butylperoxyoctate,t-butylperoxybenzoate, cuminehydroperoxide, and cumylperoxide. All ofthe radical reactions of scheme 3 are performed in the presence of asolvent, and preferably the solvent can be one or more compoundsselected from the group consisting of N,N-dimethylformamide,N,N-dimethylacetamide, dimethylsulfoxide, xylene, tetrahydrofuran,benzene, toluene, acetonitrile, dichloromethane, ethylacetate,butylacetate, 1,4-dioxane, and chloroform. Also, in the manufacture ofthe compound of formula 5, monomer Y with regard to the compound offormula 1 can be reacted in a ratio of 1:1 to 1:100.

Also, the present invention provides other antimicrobial polymericcompounds by binding the antimicrobial monomer of formula 1 to a linkerand then reacting it with a polyol.

It is preferred that the antimicrobial polymeric compounds are compoundsrepresented by formula 6 to 9 below, comprising a linker.

The linker is preferably selected from the group consisting of acompound of acid anhydride, haloacylhalogenade, and isocyanate (—N═C═O)classes. It is preferred that the isocyanate class linker is typicallyselected from the group consisting of toluenediisocyanate (TDI),dodecylisocyanate (DDI), hexamethylenediisocyanate (HDI), andtrihexamethyleneisocyanuratetriisocyanate(HMTI).

In the above formula 6 to 9, R′ is as defined above.

The manufacture of the compounds of formula 6 to 9 of the presentinvention is performed by chemically binding the functional group of thecompound of formula 1 to the isocyanate group of the linker and thenbinding it to a commonly-used polyol, as shown in scheme 4 and scheme 5,below. Typical polyols include BURNOCK (Aekyung Chemical, Co., Ltd.),ALKYLATE (Aekyung Chemical, Co., Ltd.), 045-093 (Aekyung Chemical, Co.,Ltd.), Acryl (Kukdo Chemical, Co., Ltd.), Alkyde class polyol (KukdoChemical, Co., Ltd.), etc.

All of the above reactions are performed in the presence of a solvent,which is one or more compounds selected from the group consisting ofN,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, xylene,tetrahydrofuran, benzene, toluene, acetonitrile, dichloromethane,ethylacetate, butylacetate, 1,4-dioxane, and chloroform.

A preferred embodiment of manufacture of the anti-microbial monomers andanti-microbial polymers of the present invention is as follows.

The compound of formula 1, which will be illustrated, is1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

That is, in formula 1,

R is an alkyl group comprising a hydroxy group, an ester bond, and adouble bond of 7 carbon atoms (CH2=C(CH3)—CO—O—CH2—CH(OH)—CH—);

-   -   R₁ and R₂ are H;    -   R₃ is F;    -   R₄ is H;    -   R₅ is an ethyl group;    -   R₆ is H;    -   R₈, R₉, and R₁₀ are each C; and

R₁₁ is H.

(1) Manufacture of1-Ethyl-6-Fluoro-1,4-Dihydro-7-[4-(2-Hydroxy-6-Methyl-4-Oxa-5-Oxo-6-Heptenyl)-1-Piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid

1-Ethyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid, which is the compound of formula 2, andglycidylmethacrylate, which is the compound of formula 3a, are heated at70 to 80 DC and subjected to epoxide ring-opening reaction to therebymanufacture1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid (hereinafter referred to as “Compound A”).

(2) Manufacture of Compound of Formula 4 (Anti-Microbial Polymer)

The initiator, benzoylperoxide, is added to the above compound A in thepresence of N,N-dimethylformamide, and the radical polymerization isconducted at 70 to 80° C. to thereby manufacture the anti-microbialpolymer.

(3) Manufacture of Compound of Formula 5 (Antimicrobial Polymer)

The above compound A is radically copolymerized with amethylmethacrylate monomer to thereby manufacture the compound offormula 5, poly(A-co-methylmethacrylate).

(4) Manufacture of Compounds of Formula 6 to 9 (Antimicrobial Polymer)

Compound A is reacted with toluenediisocyanate (TDI),dodecyldiisocyanate (DDI), hexamethylenediisocyanate (HDI), ortrihexamethyleneisocyanuratetriisocyanate (HMTI) in an equivalent ratioof 1:1.5, mixed with a polyol selected from BURNOCK, ALKYLATE, 045-093,etc., and reaction is performed with the temperature change of 20 to150° C. to thereby manufacture the antimicrobial polymers.

Also, the present invention provides an acrylic copolymer of formula 10using a compound of formula 11 manufactured using the compound offormula 2.

The acrylic copolymer of formula 10 of the present invention can bemanufactured by the radical reaction of the compound of formula 11 withthe compound of formula 12 below (Scheme 6).

In the above scheme 6, R12 to R14 and X are each as defined above.

The compound of formula 11 can be obtained by epoxide ring-openingreaction of the compound of formula 2 with an epoxide compound having adouble bond. The epoxide compound having a double bond is typicallyglycidylmethacrylate.

It is preferred that the compound of formula 12 has an acrylic monomer,which is the hydrocarbon chain attributed to an acrylic acid ormethacrylic acid, as a main chain. More preferably, it is a monomerhaving an acrylic acid, acrylic acid alkyl ester, methacrylic acid, ormethacrylic acid alkyl ester. The acrylic acid alkyl ester andmethacrylic acid alkyl ester preferably include a C₁˜C₁₈ alkyl. Examplesof such acrylic acid alkyl ester include methylacrylate, ethylacrylate,n-propylacrylate, isopropylacrylate, cyclohexylacrylate,t-butylcyclohexylacrylate, stearylacrylate, and laurylacrylate. Also,the acrylic monomer can comprise a reactive functional group, and asexamples of such functional groups, there are an amide group, a hydroxylgroup, an epoxy group, a silanol group, and an aldehyde group. Asacrylic monomers further comprising more specific reactive functionalgroups, there are acrylamide, metharcylamide, N-methylacrylamide,N-methylolacrylamide, N-butoxymethylacrylamide, N-methylmethacrylamide,N-butoxymethylmethacrylamide, hydroxyethylacrylate,hydroxyethylmethacrylate, hydroxypropylacrylate, hydroxypropylacrylate,hydroxypropylmethacrylate, glycidylacrylate, glycidylmethacrylate,y-trimethoxysilanemethacrylate, y-triethoxysilanemethacrylate, acrolein,caprolactone modified hydroxyacrylate, and caprolactone modifiedhydroxymethacrylate.

In the above scheme 6, any known initiators can be used, and they can beselected from the group consisting of azo-bis-iso-butylnitrile (AIBN),azobisdimethylbeleronitrile, benzoylperoxide, t-butylhydroperoxide,t-butylperoxyoctanate, t-butylperoxybenzoate, cuminehydroperoxide, andcumylperoxide. The initiators can be added in an amount of 0.05 to 10parts by weight with regard to 100 parts by weight of the totalcompound, and preferably 0.3 to 5 parts by weight. The reactiontemperature may be, but is not limited to, 50° C. to 130° C.

The compound of formula 1 and the polymeric compound comprising it ofthe present invention can be utilized for medical supplies, consumergoods, or products for industrial purposes. In particular, they can beapplied to interior materials such as blinds, wall paper, and floorcoverings; food-related products such as films for wrapping, containersfor storing, and cutting boards; appliances such as humidifiers,washers, and dish washers; engineering materials such as water supplyand drain pipes, and concrete; core materials in medical fields; andproducts for industrial purposes such as coatings. They can beparticularly useful and they are preferably used in medical supplies,that is, medical devices/products for insertion into the human body suchas catheters for medical purposes, artificial kidney apparatus,ventilating tubes for eardrums, cases for microbionic chip parts forinsertion into a human body, prostheses, products for fixing bones, orfor blood transfusion bags.

Therefore, the present invention provides an antimicrobial polymericresin composition in which one or more antimicrobial polymers selectedfrom the group consisting of the antimicrobial monomer compound offormula 1, the antimicrobial homopolymer of formula 4, the antimicrobialcopolymer compound of formula 5, the compounds of formula 6 to 9, andthe acrylic copolymer of formula 10 are uniformly mixed with an ordinarypolymeric resin.

According to the present invention, the compound of formula 1 orpolymeric compounds comprising it can be used as an additive forconventional polymeric resins to confer anti-microbial characteristicsto the resins.

The antimicrobial polymeric resin comprising the antimicrobial compoundof the present invention has a maximum release rate in water of 50ppm/100 hrs, and preferably 10 ppm/100 hrs.

The antimicrobial compound can be included in an amount of 0.1 to 30% byweight with regard to the total composition, and the polymeric resin isincluded in the remaining amount.

The polymeric resins are preferably known polymeric resins, and forexample, there are polyvinylalcohol, polyacrylonitrile, polybutadiene,polyacrylic acid, polyacrylimide, polysulfone, polyacetal, polyimide,polytetrafluoroethylene, polyneophrene, polydimethylsiloxane,polymethylmethacrylate, polyetheretherketone, polyphenylenesulfide,polyvinylfluoride, polyvinylacetate, polyetherimide,polyvinyllidinefluoride, polyethersulfone, urethane (urethane resinusing isocyanates such as 2,4-toluenediisocyanate,trihexamethyleneisocyanuratetriisocyanate, etc.), silicon resin, andnatural rubber.

Also, the present invention can use the above compounds in a combinationof acrylic light-curable oligomers. That is, the invention can provide alight-curable resin composition comprising an acrylic light-curableoligomer, a property-fortified monomer, a light initiator, and anadditive in which the light-curable resin composition comprises one ormore antimicrobial polymers selected from the group consisting of theantimicrobial monomer compound of formula 1, the antimicrobialhomopolymer of formula 4, the antimicrobial copolymer compound offormula 5, and the compounds of formula 6 to 9.

As the light-curable oligomer, acrylic resins having at least two ormore acrylic groups are used, and particularly, urethane acrylate,polyester acrylate, epoxy acrylate, or silicon acrylate (Trademarks EB284, 9269, 1290, 5129 of UCB Co.; CN 963, 966 of Sartomer Co., etc.) canbe used.

As the property-fortified monomer, hydroxypropyl acrylate (HPA),1,6-hexanedioldiacrylate (HDDA), pentaerythritol triacrylate (PETA),polyethyleneglycoldiacrylate (PEGDA), trimethylolpropane ethoxylatetriacrylate (TMPEOTA), or dipentaerythritol hexaacrylate (DPHA) can beused.

As the light initiator, 1-hydroxycyclohexylphenylketone (CibaGeigy,Irgacure 184) or Irgacure 500 in which Irgacure 184 is mixed withbenzophenone in a ratio of 1:1 can be used.

As the additive for the improvement of smoothness, BYK 307 or BYK 310(BYK Chemical) is used, and it can be used in an amount of 0.2 to 0.4%by weight based on the total resin. Also, as a diluent, ethanol,methanol, 2-propanol, butanol, or butylacetate can be used.

The antimicrobial polymeric resin compositions of the present inventioncan further comprise EBS or polyethylene wax as an additive when molded,and more preferably, it can comprise a polyethylene wax in an amount of0.1 to 10% by weight.

Also, as methods for using the compound of formula 1 or the polymericcompound using it of the present invention in the polymeric resins,there are injection and extrusion molding, and blowing or laminatingtreatment methods after their direct addition during the molding processof plastics or their addition in the form of a master batch. Of them,the direct addition method includes steps of mixing the antimicrobialcompounds with natural rubbers, synthetic rubbers, or polymeric resins,and then injection and extrusion molding, blowing, and laminate molding.The addition method in the form of a master batch includes thepreparation of the master batch by mixing the antimicrobial substanceswith low-density polyethylene (LDPE), linear low-density polyethylene(LLDPE), high-density polyethylene (HDPE), polypropylene (PP),polyvinylchloride (PVC), polyurethane (PU), ABS, SAN, PCL, PC, silicon,or synthetic rubbers, and then extrusion molding; and the processes ofmixing the above prepared master batch with an ordinary polymeric resinand injection and extrusion molding, blowing, and laminate molding.

It is preferred that the content of the compound of formula 1 or thepolymeric compounds comprising it used in the preparation of the masterbatch is 0.1 to 30 parts by weight with regard to 100 parts by weight ofthe total composition. If the content of the compound of formula 1 orthe polymeric compounds comprising it is less than 0.1 parts by weight,the anti-microbial effects are insignificant, and if it exceeds 30 partsby weight, the properties might not be good.

Hereafter, the examples of the present invention will be described. Thefollowing examples are provided solely to illustrate the presentinvention: the protection scope of the present invention is not limitedthereto.

EXAMPLE 1 Manufacture of{1-Cyclopropyl-6-Fluoro-1,4-Dihydro-7-[4-(10,11-Epoxy-2,6-Dihydroxy-4,8-Dioxaundecyl)-3-Methyl-1-piperazinyl]-5-Methyl-4-Oxo-3-QuinolineCarboxylic Acid}

15.0 ml of N,N-dimethylformamide were charged into a round 3-neck flaskof 50 ml equipped with a thermometer and a stirring device, and 30.4 mgof1-cyclopropyl-6-fluoro-1,4-dihydro-5-methyl-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were added thereto and they were slowly stirred at roomtemperature for 10 minutes. 17.2 mg of glyceroldiglycidylether wereadded thereto and stirred. The reactants were washed with 1.2 ml ofN,N-dimethylformamide, and they were reacted for 5 hours after theirtemperature was adjusted to 60° C. Thereafter, after cooling, they werestirred at 20° C. for 10 minutes. The reactants were obtained in acrystalized state from the layer of water and then dried to give 35.0 mgof1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(10,11-epoxy-2,6-dihydroxy-4,8-dioxaundecyl)-3-methyl-1-piperazinyl]-5-methyl-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (DMSO-d₆) δ 1.05 (3H, d), 1.20˜1.44 (4H, m), 2.40 (3H, s),2.50˜3.00 (7H, m), 3.10˜4.00 (16H, m), 7.39 (1H, d), 8.81 (1H, s).

EXAMPLE 2 Manufacture of{1-Ethyl-6,8-Difluoro-1,4-Dihydro-7-[4-(2-Hydroxy-6-Methyl-4-Oxa-5-Oxo-6-Heptenyl)-3-Methyl-1-Piperazinyl]-4-Oxo-3-Quinoline Carboxylic Acid}

39.4 mg of1-ethyl-6,8-difluoro-1,4-dihydro-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were mixed with 10.0 ml of 2,6-dimethylpiperazine in around flask of 50 ml and slowly stirred at room temperature for 10minutes. 22.0 mg of glycidylmethacrylate were added thereto and stirredat room temperature, and then the reactants were washed with 2.0 ml of2,6-dimethylpiperazine. Thereafter, the reaction was performed at 40° C.for 8 hours, and after the temperature was reduced to room temperature,the reaction was performed for another 8 hours. The crystalizedreactants were obtained from the layer of water and dried to give 25 mgof1-ethyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3-methyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (DMSO-d₆) δ 1.10 (3H, d), 1.58 (3H, t), 1.93 (3H, s), 2.52˜3.00(5H, m), 3.23˜3.41 (4H, m), 3.90˜4.38 (5H, m), 5.58 (1H, d), 6.15 (1H,d), 7.72 (1H, s), 8.62 (1H, s)

EXAMPLE 3 Manufacture of{8-Ethyl-5,8-Dihydro-2-{4-[2-Hydroxy-3-(4-Nonylphenoxy)Propyl]-1-piperazinyl}-5-Oxopyrido[2,3-d]Pyrimidine-6-CarboxylicAcid}

38.0 mg of8-ethyl-5,8-dihydro-5-oxo-2-(1-piperazinyl)pyrido{2,3-d}pyrimidine-6-carboxylicacid were mixed with 12.0 ml of dimethylsulfoxide in a round flask of 50ml and slowly stirred at room temperature for 10 minutes. 18.0 mg ofglycidylnonylphenylether were added thereto, it was stirred again atroom temperature, and then washed with 12 ml of dimethylsulfoxide. Thereactants were placed at 50° C. for 11 hours, and then stirred at 20° C.for 10 minutes. The reactants were crystalized from isopropyl alcoholand the layer of water with methylene chloride, filtered, and then driedto give 37.2 mg of8-ethyl-5,8-dihydro-2-{4-[2-hydroxy-3-(4-nonylphenoxy)propyl]-1-piperazinyl}-5-oxopyrido[2,3-d]pyrimidine-6-carboxylic acid.

¹H-NMR (DMSO-d₆) δ 0.88 (3H, t), 1.10˜1.70 (17H, m), 2.45˜3.05 (10H, m),3.35˜3.55 (4H, m), 3.92˜4.12 (3H, m), 6.76, 7.05 (4H, ABq), 8.58 (1H,s), 8.87 (1H, s).

EXAMPLE 4 Manufacture of{Cis-5-Amino-1-Cyclopropyl-6,8-Difluoro-1,4-Dihydro-7-[4-(2-Hydroxy-6-Methyl-4-Oxa-5-Oxo-6-Heptenyl)-3,5-Dimethyl-1-piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid}

43.7 mg ofcis-5-amino-1-cyclopropl-6,8-difluoro-1,4-dihydro-7-(3,5-dimethyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were mixed with 5.0 ml of N,N-dimethylacetamide in around flask of 50 ml and slowly stirred at room temperature for 10minutes. 17.5 mg of glycidylmethacrylate were added thereto, it wasstirred at room temperature, and then washed with 3.1 ml ofN,N-dimethylacetamide. The reactants were held at 75° C. for 6 hours andthen stirred at 20° C. for 10 minutes. Thereafter, the reactants werecrystalized from isopropyl alcohol and the layer of water with methylenechloride, filtered, and then dried to give 29.3 mg ofcis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3,5-dimethyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (DMSO-d₆) δ 1.07 (6H, d), 1.20˜1.45 (4H, m), 1.96 (3H, s),2.50˜3.00 (4H, m), 3.20˜3.60 (5H, m), 4.00˜4.40 (3H, m), 5.67 (1H, s),6.20 (1H, s), 8.60 (1H, s).

EXAMPLE 5 Manufacture of{1-(2,4-Difluorophenyl)-6-Fluoro-1,4-Dihydro-7-[4-(2-Hydroxy-5-Methyl-4-Oxa-5-Oxo-6-Heptenyl)-3-Methyl-1-Piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid}

49.2 mg of1-(2,4-difluorophenyl)-6-fluoro-1,4-dihydro-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were mixed with 10.0 ml of N,N-dimethylformamide in around flask of 50 ml and stirred at room temperature for 10 minutes.14.3 mg of glycidylmethacrylate were added thereto, it was stirred atroom temperature, and then washed with 5.0 ml of N,N-dimethylformamide.The reactants were held at 80° C. for 9 hours and then stirred at 20° C.for 10 minutes. The reactants were filtered as a crystal from isopropylalcohol and the layer of water after application of methylene chloride,and then dried to give 41.0 mg of1-(2,4-difluorophenyl)-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-5-methyl-4-oxa-5-oxo-6-heptenyl)-3-methyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (DMSO-d₆) δ 1.06 (3H, d), 1.95 (3H, s), 2.50˜3.00 (5H, m),3.20˜3.40 (4H, m), 4.00˜4.40 (3H, m), 5.58 (1H, s), 6.15 (1H, s),6.45˜6.85 (4H, m), 7.89 (1H, d), 8.62 (1H, s).

EXAMPLE 6 Manufacture of{1-Cyclopropyl-6-Fluoro-7-[4-(3-Dodecafluoro-2-Hydroxy-4-Oxaundecyl)-3-Methyl-1-Piperazinyl]-1,4-Dihydro-5-Methyl-4-Oxo-3-Quinoline Carboxylic Acid}

39.4 mg of1-cyclopropyl-6-fluoro-5-methyl-1,4-dihydro-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were added to 12.2 ml of N,N-dimethylformamide in around flask of 50 ml and slowly stirred at room temperature for 10minutes. 37.3 mg of glycidyldodecafluoroheptylether were added thereto,it was stirred at room temperature, and then washed with 12.2 ml ofN,N-dimethylformamide. The reactants were held at 70° C. for 6 hours andthen stirred at 20° C. for 10 minutes. The reactants were crystalizedfrom isopropyl alcohol and the layer of water with ether, filtered,washed with hexane, and then dried to give 43.1 mg of1-cyclopropyl-6-fluoro-7-[4-(3-dodecafluoro-2-hydroxy-4-oxaundecyl)-3-methyl-1-piperazinyl]-1,4-dihydro-5-methyl-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (DMSO-d₆) δ 1.06 (3H, d), 1.20˜1.45 (4H, m), 2.40 (3H, s),2.50˜3.00 (5H, m), 3.20˜4.10 (10H, m), 5.80˜6.20 (1H, m) 7.40 (1H, d),8.82 (1H, s).

EXAMPLE 7 Manufacture of{1-Ethyl-6,8-Difluoro-1,4-Dihydro-7-{4-[2-Hydroxy-3-(Methoxy)Phenoxypropyl]-3-Methyl-1-piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid]

30.4 mg of1-ethyl-6,8-difluoro-1,4-dihydro-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were mixed with 13.0 ml of N,N-dimethylformamide in around flask of 50 ml and slowly stirred at room temperature for 10minutes. 19.7 mg of glycidyl-4-methoxyphenylether were added thereto, itwas stirred at room temperature, and then washed with 10.2 ml ofN,N-dimethylformamide. The reactants were held at 80° C. for 7 hours andstirred at 15° C. for 5 minutes. Thereafter, the reactants werecrystalized from the ethyl alcohol phase and the layer of water withdioxane, filtered, washed with hexane and then dried to give 17.3 mg of1-ethyl-6,8-difluoro-1,4-dihydro-7-{4-[2-hydroxy-3-(methoxy)phenoxypropyl]-3-methyl-1-piperazinyl}-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (DMSO-d₆) δ 1.06(3H, d), 1.58 (3H, t), 2.50˜3.00 (5H, m),3.20˜3.40 (4H, m), 3.70 (3H, s), 3.90˜4.40 (5H, m), 6.60˜6.80 (4H, m),7.68 (1H, s), 8.60 (1H, s).

EXAMPLE 8 Manufacture of {1-Ethyl-6-Fluoro-1,4-Dihydro-7-{4[2-Hydroxy-3-(Toluene-4-Sulfonyloxy)-Propyl]-1-Piperazinyl}Oxo-3-QuinolineCarboxylic Acid}

39.4 mg of1-ethyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were mixed with 50 ml of N,N-dimethylformamide in around flask of 100 ml and slowly stirred at room temperature for 20minutes. 14.4 mg of glycidyl tosylate were added thereto, it was stirredat room temperature, and then washed with 30.0 ml ofN,N-dimethylformamide. The reactants were held at 80° C. for 5 hours andthen stirred at 25° C. for 10 minutes. The reactants were crystalizedthrough column chromatography (20 gm silica, 10% ethylacetate/hexane),filtered, and then dried to give 11.2 mg of1-ethyl-6-fluoro-1,4-dihydro-7-{4-[2-hydroxy-3-(toluene-4-sulfonyloxy)-propyl]-1-piperazinyl}-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (DMSO-d₆) δ 1.60 (3H, t), 2.40 (3H, s), 2.50˜2.85 (6H, m),3.20˜3.40 (4H, m), 3.90˜4.40 (5H, m), 6.82 (1H, d), 7.40˜7.85 (5H, m),8.60 (1H, s).

EXAMPLE 9 Manufacture of{1-Cyclopropyl-6-Fluoro-1,4-Dihydro-7[4-(2-Hydroxy-6-Methyl-4-Oxa-5-Oxo-6-Heptenyl)-1-piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid}

39.4 mg of1-cyclopropyl-6-fluoro-1,4-dihydro-7-(1-piperazinl)-4-oxo-3-quinolinecarboxylic acid were mixed with 50 ml of N,N-dimethylacetamide in around flask of 100 ml and slowly stirred at room temperature for 30minutes. 17.5 mg of glycidylmethacrylate were added thereto, it wasstirred at room temperature, and then washed with 1.2 ml ofN,N-dimethylacetamide. Thereafter, the reactants were held at 80° C. for19 hours, stirred at 25° C. for 30 minutes, and then crystalized fromisopropyl alcohol and the layer of water with methylene chloride andfiltered. The filtrates were dried to give 53.3 mg of1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (CDCl₃) δ 1.20˜1.41 (4H, m), 2.05 (3H, s), 2.51 (2H, d), 2.59(2H, t), 2.85 (2H, d), 3.25˜3.60 (5H, m), 4.05 (2H, m), 4.30 (1H, m),5.58 (1H, s), 6.15 (1H, s), 7.28 (1H, d), 8.05 (1H, d), 8.80 (1H, s)

EXAMPLE 10 Manufacture of{1-Ethyl-6-Fluoro-1,4-Dihydro-7-[4-(2-Hydroxy-6-Methyl-4-Oxa-5-Oxo-6-Heptenyl)-1-Piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid}

39.4 mg of1-ethyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were added to 50 ml of N,N-dimethylacetamide in a roundflask of 100 ml and slowly stirred at room temperature for 10 minutes.17.5 mg of glycidylmethacrylate were added thereto, it was stirred atroom temperature, and then washed with 11.2 ml of N,N-dimethylacetamide.Thereafter, the reactants were held at 80° C. for 15 hours and thenstirred at 25° C. for 1 hour. The reactants were passed through columnchromatography (20 gm silica, 10% ethylacetate/hexane), crystalized fromisopropylalcohol and the layer of water with methylene chloride, andthen filtered. The filtrates were dried to give 36 mg of1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (CDCl₃) δ 1.48 (3H, t), 1.93 (3H, s), 2.51 (2H, d), 2.59˜2.82(4H, m), 3.10˜3.40 (4H, t), 3.45 (2H, m), 3.90˜4.28 (4H, m), 5.58 (1H,d), 6.05 (1H, d), 6.75 (1H, S), 7.62 (1H, d), 8.58 (1H, s)

EXAMPLE 11 Manufacture of{8-Ethyl-5,8-Dihydro-2-[4-(2-Hydroxy-6-Methyl-4-Oxa-5-Oxo-6-Heptenyl)-1-piperazinyl]-5-oxo-Pyrido[2,3-d]Pyrimidine-6-CarboxylicAcid}

38.2 mg of8-ethyl-5,8-dihydro-5-oxo-2-(1-piperazinyl)-pyrido[2,3-d]pyrimidine-6-carboxylicacid were mixed with 50 ml of N,N-dimethylacetamide in a round flask of100 ml and slowly stirred at room temperature for 50 minutes. 15.0 mg ofglycidylmethacrylate were added thereto, it was stirred at roomtemperature, and then washed with 10 ml of N,N-dimethylacetamide.Thereafter, the reactants were held at 70° C. for 15 hours and thenstirred at 20° C. for 1 hour. The reactants were passed through columnchromatography (20 gm silica, 10% ethylacetate/hexane), crystalized fromisopropyl alcohol and the layer of water with methylene chloride,filtered, and then dried to give 27 mg of8-ethyl-5,8-dihydro-2-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-5-oxo-pyrido[2,3-d]pyrimidine-6-carboxylicacid.

¹H-NMR (DMSO-d₆) δ 1.58 (3H, s), 1.95 (3H, s), 2.50˜2.85 (6H, m),3.20˜3.50 (4H, m), 3.90˜4.40 (5H, m), 5.60 (1H, s), 6.14 (1H, s), 8.62(1H, s), 8.87 (1H, s).

EXAMPLE 12 Manufacture of{1-Ethyl-6-Fluoro-1,4-Dihydro-7-[4-(1-Oxo-2-Propenyl)-1-piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid}

Under nitrogen conditions, 30 ml of chloroform were added to 500 mg(1.567 mmol) of1-ethyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid in a round flask of 50 ml, into which 0.436 ml (3.134mmol) of triethylamine was then charged and stirred at room temperaturefor 10 minutes. While the inside temperature of the container wasmaintained at −10° C., 0.127 ml (1.567 mmol) of acrylochloride wasslowly dripped thereinto and reacted. The reaction was conducted undernitrogen at −10° C. for 3 hours, then distilled water was added to thereactants, which were then extracted with dichloromethane. The extractswere concentrated and then chromatographed (20 gm silica, 7%MeOH/CH₂Cl₂) to give1-ethyl-6-fluoro-1,4-dihydro-7-[4-(1-oxo-2-propenyl)-1-piperazinyl]4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (CDCl₃) δ 1.48 (3H, t), 3.20 (4H, t), 3.42 (4H, t), 4.32 (2H, q),5.55 (1H, t), 6.12 (1H, t), 6.62 (1H, t), 7.02 (1H, s), 7.75 (1H, s),8.85 (1H, s)

EXAMPLE 13 Manufacture of{1-Cyclopropyl-6-Fluoro-1,4-Dihydro-7-[4-(2-Methyl-1-Oxo-2-Propenyl)-1-piperazinyl]-4-Oxo-3-QuinolineCarboxylic Acid}

700 mg (2.024 mmol) of1-cyclopropyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were added to a round 3-neck flask of 50 ml under anitrogen atmosphere, and then stirred at room temperature for 10 minutesafter 30 ml of chloroform and 0.491 ml (3 mmol) of pyridine were addedthereto. While the temperature of the inside of the container was keptat −10° C., 0.197 ml (2.024 mmol) of methacryloylchloride was slowlydripped thereinto. After reaction for 3 hours, distilled water was addedto the reactants, which were then extracted with dichloromethane,concentrated, and chromatographed (20 gm silica, 7% MeOH/CH₂Cl₂) to give1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-methyl-1-oxo-2-propenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

¹H-NMR (CDCl₃) δ 1.20 (2H, m), 1.41 (2H, m), 2.00 (3H, s), 3.30 (4H, t),3.35 (1H, m), 3.50 (1H, m), 3.95 (2H, d), 5.20 (2H, d) 7.42 (1H, d),8.00 (1H, d), 8.90 (1H, s)

EXAMPLE 14 Manufacture of{1-Ethyl-6-Fluoro-1,4-Dihydro-7-[4-(4-Vinylbenzyl)-1-piperazinyl]-4-Oxo-3-QuinolineCarboxylic acid}

Under a nitrogen atmosphere, 400 mg (1.252 mmol) of1-ethyl-6-fluoro-1,4-dihydro-7-(1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid were mixed with 0.349 ml (2.505 mmol) of triethylaminein a round flask of 50 ml and stirred at room temperature for 10minutes. While the temperature of the inside of the container was keptat −10° C., 0.177 ml (1.252 mmol) of vinylbenzylchloride was slowlydripped thereinto. Under a nitrogen atmosphere, the reaction wasconducted for three hours while keeping the temperature at −10° C., andthen distilled water was added to the reactants which were thenextracted with dichloromethane. The extracts were concentrated and thenchromatographed (20 gm silica, 5% MeOH/CH2Cl2) to give 501 mg (91.9%) of1-ethyl-6-fluoro-1,4-dihydro-7-[4-(4-vinylbenzyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid.

¹H NMR (CDCl₃) δ 1.48 (3H, t), 3.20 (4H, t), 3.42 (4H, t), 4.55 (2H, q),5.18 (2H, s), 5.61 (2H, d), 6.63 (1H, m) 7.01 (2H, d), 7.10 (1H, d),7.18 (2H, d), 7.81 (1H, d), 8.87(1H, s)

EXAMPLE 15 Manufacture of Compound of Formula 4

750 mg of1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid were dissolved in 30 ml of N,N-dimethylacetamide in around flask of 50 ml and stirred at room temperature for 10 minutes. 20mg of AIBN were added to the reactants, which were then reacted at 70°C. for 4 hours and then cooled to room temperature. The resultantreactants were slowly added to 100 ml of cold water, which was preparedin advance, and then stirred at room temperature for 30 minutes andfiltered to thereby yield crystals. They were dried to give the compoundof formula 4.

EXAMPLE 16 Manufacture of Compound of Formula 5

0.5 g (1.251 mmol) of1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid were dissolved in 30 ml of N,N-dimethylformamide in around flask of 50 ml and then stirred at room temperature for 10minutes. 10 g (138.77 mmol) of acrylic acid were added to the reactants,which were then reacted at room temperature for 10 minutes, and then0.05 g of benzoylperoxide was slowly dripped thereinto. Subsequently,after the temperature was raised to 80° C., the reaction was performedfor 4 hours followed by cooling to room temperature. 100 ml of coldwater, which was prepared in advance, was slowly added to the reactantswhile stirring, and the solids were filtered and dried to give the titlecompound.

EXAMPLE 17 Manufacture of Compound of Formula 5a

4.5 g (62.44 mmol) of acrylic acid were charged into a 500 ml 3-neckflask, 100 ml of toluene were added thereto, and then 0.5 g (1.083 mmol)of1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid of Example 9 was added. Under a nitrogen atmosphere,after the temperature was raised to 40° C., the reactants were stirred,0.1 g of BPO was added thereto, and then the temperature was slowlyraised to 80° C. again. The reactants were held at 80° C. for 2 hoursand 40 minutes, cooled again to room temperature, and then filteredunder a reduced pressure to thereby yield white solids. They were washedwith ether and then dried to give 4.75 g of the antimicrobial acrylicacid copolymer (95% yield).

EXAMPLE 18 Manufacture of Compound of Formula 5a

15.6 g (216.6 mmol) of acrylic acid were charged into a 500 ml 3-neckflask, 100 ml of toluene were added thereto and dissolved, and then 10 g(21.66 mmol) of1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid of Example 10 were added thereto and stirred under anitrogen gas condition after raising the temperature to 40° C. 0.5 g ofAIBN was added thereto, and after the temperature was raised to 80° C.,the reaction was conducted for 3 hours and 10 minutes while keeping thetemperature at 80° C. The obtained white solids were filtered under areduced pressure, washed with ether, and then dried to give 24.627 g ofthe antimicrobial acrylic acid copolymer (96.2% yield).

EXAMPLE 19 Manufacture of Compound of Formula 5b

15.6 g (119.8 mmol) of HEMA (2-hydroxyethylmethacrylate) and 50 ml ofDMSO were charged into a 500 ml 3-neck flask, and 10.21 g (21.6 mmol) of1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid of Example 9 were added thereto and completely dissolvedby heating it to 40° C. 0.5 g of AIBN were added to the dissolvedreactants while stirring under a nitrogen gas condition, and thetemperature was raised to 75° C. and then the reactants were placed forthree hours. The produced light-yellow solids were filtered under areduced pressure, washed with ether, and dried to give 25.16 g of theantimicrobial acrylic copolymer (97.66% yield).

EXAMPLE 20 Manufacture of Compound of Formula 5c

2 g (23.49 mmol) of methacrylicamide and 50 ml of DMF were charged intoa 500 ml 3-neck flask, and then 5.42 g (11.44 mmol) of the compound ofExample 9 were added thereto. 0.1 g of BPO was added to the reactants,which were then reacted under a nitrogen gas condition at 75° C. forthree hours. The reactants were solidified in water, filtered under areduced pressure, stirred three times with acetone 100 for 10 minutes,and then filtered and dried to give 7.22 g of the antimicrobialmethacrylicamide copolymer in the form of light yellow solids (97.4%yield).

EXAMPLE 21 Manufacture of Compound of Formula 5d

5.0 g (58.74 mmol) of methacrylicamide and 70 ml of DMF were added to a500 ml 3-neck flask in turn and completely dissolved. 2.71 g (5.874mmol) of the compound of Example 10 and 0.19 g of BPO were added theretoand heated to 75° C. under a nitrogen gas condition while stirring. Thereactants were reacted at 75° C. for 2 hours and 10 minutes and thencooled. 100 ml of toluene was added thereto to produce light yellowprecipitates, which were then filtered under a reduced pressure anddried to give 7.60 g of the antimicrobial methacrylamide copolymer(98.6% yield).

EXAMPLE 22 Manufacture of Compound of Formula 5f

10 g (99.88 mmol) of methylmethacrylate and 360 ml ofN,N-dimethylacetamide were added to a 500 ml 3-neck flask in turn andcompletely dissolved. Thereafter, 47.29 g (99.88 mmol) of the compoundof Example 9 and 1.682 g of AIBN were added thereto while stirring undera nitrogen gas condition. After the temperature was raised to 75° C.,the reaction was conducted for 6 hours, and then the temperature wascooled to room temperature and the reactants were solidified in 1000 mlof cold water. The solids were filtered under a reduced pressure, washedwith 450 ml of acetone three times for 5 minutes, and then dried to give54.69 g of the antimicrobial acrylic copolymer in the form of yellowsolids (95.5% yield).

EXAMPLE 23 Manufacture of Compound of Formula 5g

10 g (99.88 mmol) of methylmethacrylate and 360 ml ofN,N-dimethylacetamide were added to a 500 ml 3-neck flask in turn andcompletely dissolved. 47.292 g (99.88 mmol) of the compound of Example10 and 1.7189 of AIBN were added thereto. Thereafter, the reactants werereacted while stirring under a nitrogen gas condition for 6 hours afterthe temperature was raised to 75° C. The reactants were cooled to roomtemperature and solidified in 1000 ml of cold water, and then filteredunder a reduced pressure. The filtrates were washed with 450 ml ofacetone three times for 5 minutes and dried to give 56.396 g of theantimicrobial acrylic copolymer in the form of yellow solids (98.43%yield).

Further, according to the same methods as in Examples 15 to 23 above,the compounds of formula 4 and 5 were manufactured respectively, using1-ethyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3-methyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3,5-dimethyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,1-(2,4-difluorophenyl)-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-5-methyl-4-oxa-5-oxo-6-heptenyl)-3-methyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,8-ethyl-5,8-dihydro-2-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-5-oxo-pyrido[2,3-d]pyrimidine-6-carboxylicacid,1-ethyl-6-fluoro-1,4-dihydro-7-[4-(1-oxo-2-propenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid, or1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-methyl-1-oxo-2-propenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid, and using AIBN or benzoylperoxide as an initiator.

EXAMPLE 24 Manufacture of Linker-Binding Type Antimicrobial Monomer I

0.840 mg of1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid and 30 ml of benzene were charged into a 500 ml 3-neckand dissolved at 50° C., and then 0.635 mg of tolylene 2,4-diisocyanateand 0.01 mg of dibutyltindiolate (DBTDL) were added thereto and stirredat 60° C. for 2 hours. 0.213 mg of isopropylalcohol was added to thereactants, which were then stirred at 60° C. for 5 hours to therebycomplete the reaction. After the reactants' temperature was cooled toroom temperature, the reaction solvents were eliminated by distillationunder a reduced pressure and the reaction products were chromatographed(20 mg silica, 10% ethylacetate/hexane) to give the antimicrobialcompound.

EXAMPLE 25 Manufacture of Linker-Binding Type Antimicrobial Monomer II

2.2 mg of1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid and 100 ml toluene were charged into a 250 ml 3-neck,and dissolved at 80° C., and then 3.7 mg oftrihexamethyleneisocyanuratetriisocyanate and 0.01 mg ofdibutyltindiolate (DBTDL) were added thereto and reacted at 110° C. for12 hours. 75 mg of isopropylalcohol were added to the reactants, whichwere stirred at 60° C. for 5 hours to thereby complete the reaction.After the reaction temperature was cooled to room temperature, thereaction solvents were eliminated by distillation under a reducedpressure and the reaction products were chromatographed (20 mg silica,10% ethylacetate/hexane) to give the antimicrobial compound.

Further, according to the same methods as in Example 24 and 25 above,1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(10,11-epoxy-2,6-dihydroxy-4,8-dioxaundecyl)-3-methyl-1-piperazinyl]-5-methyl-4-oxo-3-quinolinecarboxylic acid,1-ethyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3-methyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,8-ethyl-5,8-dihydro-2-{4-[2-hydroxy-3-(4-nonylphenoxy)propyl]-1-piperazinyl}-5-oxopyrido[2,3-d]pyrimidine-6-carboxylic acid,cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-3,5-dimethyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,1-(2,4-difluorophenyl)-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-5-methyl-4-oxa-5-oxo-6-heptenyl)-3-methyl-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,1-cyclopropyl-6-fluoro-7-[4-(3-dodecafluoro-2-hydroxy-4-oxaundecyl)-3-methyl-1-piperazinyl]-1,4-dihydro-5-methyl-4-oxo-3-quinolinecarboxylic acid,1-ethyl-6,8-difluoro-1,4-dihydro-7-{4-[2-hydroxy-3-(methoxy)phenoxypropyl]-3-methyl-1-piperazinyl}-4-oxo-3-quinolinecarboxylic acid,1-ethyl-6-fluoro-1,4-dihydro-7-{4-[2-hydroxy-3-(toluene-4-sulfonyloxy)-propyl]-1-piperazinyl}-4-oxo-3-quinolinecarboxylic acid,1-cyclopropyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid,1-ethyl-6-fluoro-1,4-dihydro-7-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-4-oxo-3-quinolinecarboxylic acid, or8-ethyl-5,8-dihydro-2-[4-(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)-1-piperazinyl]-5-oxo-pyrido[2,3-d]pyrimidine-6-carboxylicacid was bounded to toluenediisocyanate (TDI), dodecyldiisocyanate(DDI), hexamethylenediisocyanate (HDI), ortrihexamethyleneisocyanuratetriisocyanate (HMTI), respectively, as alinker to manufacture the antimicrobial monomers.

EXAMPLE 26 Antimicrobial Polymer

Each of the compounds manufactured in Examples 24 and 25 above wascombined or reacted with the polyols of Table 1 below to manufacture theantimicrobial polymers (yield: 100%). The reaction temperature wasvaried according to the polyols used, within the range of roomtemperature or 50° C. to 150° C. TABLE 1 Acrylate and AlkydpolyolCopolymer OH Value Tg Category (%) (° C.) NVM(%) Burnock* 17.5 126 50Burnock: Acrylpolyol ALKYLATE* 25 79 50 ALKYLATE: Acrylpolyol 045-093*80 97 55 Kukdo Chemical, Kukdo 23 89 50 Co.: Acrylpolyol Chemical,045-093: Alkydpolyol Co.

EXAMPLE 27 Manufacture of Antimicrobial Light-Curable Resin

Light-curable oligomers, property-fortified monomers, light initiators,and additives for the improvement of smoothness were added to theantimicrobial monomer compounds or antimicrobial polymers to manufacturethe light-curable resins.

As the light-curable oligomer, an acrylic resin having at least two ormore acrylic groups was used, and particularly, urethane acrylate,polyester acrylate, epoxy acrylate, or silicon acrylate was used(Trademarks: EB 284, 9269, 1290, 5129 of UCB Co.; CN 963, 966 ofSartomer Co., etc.).

As the property-fortified monomer, hydroxypropyl acrylate (HPA),1,6-hexanedioldiacrylate (HDDA), pentaerythritol triacrylate (PETA),polyethyleneglycoldiacrylate (PEGDA), trimethylolpropane ethoxylatetriacrylate (TMPEOTA), or dipentaerythritol hexaacrylate (DPHA) wasused.

As the light initiator, 1-hydroxycyclohexylphenylketone (CibaGeigy,Irgacure 184) or Irgacure 500 in which Irgacure 184 and benzophenonewere mixed in a ratio of 1:1 was used.

As the additive for the improvement of smoothness, BYK 307 or BYK 310(BYK Chemical) was used in an amount of 0.2 to 0.4% by weight of thetotal resin. Also, as the diluent, ethanol, methanol, 2-propanol,butanol, or butylacetate was used.

Table 2 below (units: wt. %) shows the ratios of the componentscontained in the light-curable resins. TABLE 2 Components Resin 1 Resin2 Resin 3 Resin 4 Resin 5 Resin 6 EB9269 55 50 — 45 45 — EB1290 — — 40 —— 40 DPHA — — 10 — — 10 PETA 15 5 10 5 5 10 HDDA 15 15 10 15 15 10 HPA 55 — 5 5 — IRG184 4.8 4.8 4.8 4.8 4.8 4.8 BYK310 0.2 0.2 0.2 0.2 0.2 0.2Antimicrobial Example 1 Example 5 Example Example Example ExampleMonomer/Polymer 12 15 20 23 5 20 25 25 25 25

(1) Coating Treatment

The above resins 1 to 6 were coated to a 10-um thickness (the coatingthickness in a cured state) onto polycarbonate specimens using a #7 barcoater and then cured with UV light. With regard to the coatedpolycarbonate specimens, their physicochemical properties and functionswere determined and the results are exhibited in Table 3 below. TABLE 3Item Resin 1 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Curability, goodgood good good good good 300 mJ/cm² Adhesion 100/100 100/100 100/100100/100 100/100 100/100 Ability Contamination V.G V.G V.G V.G V.G V.GResistance Anti-microbial grade 0 grade 0 grade 0 grade 0 grade 0 grade0 Characteristics Yellowing pass pass pass pass pass passCurability: Determined by comparing the coating loss after 100 frictiontests of surface methylethylketone and surface tacky properties aftercuring with the intensity of radiation of 300 mJ/cm2.Adhesion Ability: Determined by the number of coating layers remainedafter marking 100-checker board scales on resins at 1 mm width and thentaking them off with 3M scotch tape.Contamination Resistance: After marking resins with an oily pen and thenwashing them with ethanol, it was designated as V.G. if there remains nosurface mark, as G if traces remain, and as X if erasing was notpossible.Anti-microbial Characteristics: Determined according to ASTM G 21-22against all kinds of bacterial strainsAnti-yellowing: Determined according to ASTM D1925.

From Table 3 above, it can be seen that the light-curable resins of thepresent invention have excellent curability and adhesion ability, verygood contamination resistance, and high anti-microbial characteristicsand anti-yellowing.

EXAMPLE 28 Manufacture I of Antimicrobial Coating Composition

12 g of butanol, 23 g of isopropyl alcohol, 25 g of butylcellosolve and20 g of toluene were added to 1000 g of acryl resin solids (KA-961-50:Samhwa Paints Ind. Co., Ltd,), and stirred at a stirring speed of 650rpm for 20 minutes. 351 g of titanium dioxide and 11 g of a wetdispersion agent (Trademark: Disperbyk-110) were added to the reactants,which were then evenly mixed by stirring them at the same speed foranother 25 minutes, and thereafter dispersing using a sand mill. 8 g ofthe compound of Example 9 were diluted in 15 ml of the above mixture, towhich 4.3 g of anti-foaming agent (Trademark: BYK-066) and 14 g ofadhesion enhancer (Trademark: ADD-486) were added to manufacture theantimicrobial coating composition.

The antimicrobial characteristics of the above antimicrobial coatingcomposition were determined, and it was proven that the antimicrobialcoating composition of the present invention had bactericidal effectsagainst various bacteria.

EXAMPLE 29 Manufacture II of Antimicrobial Coating Composition

15 g of butanol, 25 g of isopropyl alcohol, 25 g of butylcellosolve and20 g of toluene were added to 1000 g of acryl resin solids (KA-961-50:Samhwa Paints Ind. Co., Ltd,), and stirred at a stirring speed of 650rpm for 20 minutes. 345 g of titanium dioxide and 5 g of a wetdispersion agent (Trademark: Disperbyk-110) were added to the reactants,which were then evenly mixed by stirring them at the same speed foranother 25 minutes, and thereafter dispersing using a sand mill. 10 g ofthe antimicrobial acrylic polymer of Example 20 were diluted in 20 ml ofthe above mixture, to which 3.3 g of an anti-foaming agent (Trademark:BYK-066) and 15 g of an adhesion enhancer (Trademark: ADD-486) wereadded to manufacture the coating. The antimicrobial characteristics ofthe above antimicrobial coating composition were determined and it wasproven that the antimicrobial coating composition of the presentinvention had bactericidal effects against various bacteria.

EXAMPLE 30 Manufacture III of Antimicrobial Coating Composition

The coating was manufactured using the compound of Example 10 aboveaccording to the same method as in Example 28. The obtainedantimicrobial coating composition exhibited bactericidal effects againstvarious bacteria.

EXAMPLE 31 Manufacture IV of Antimicrobial Coating Composition

The coatings were manufactured using the compounds of Example 16 to 19and 21 to 23 above, respectively, according to the same method as inExample 29. The produced antimicrobial coating compositions exhibitedbactericidal effects against various bacteria.

EXPERIMENTAL EXAMPLE 1 Manufacture of Specimen and AntimicrobialCharacteristics Determination Experiment

The specimens were manufactured with the compositional ratios (units:wt. %) shown in Table 4 below, and their antimicrobial characteristicswere determined.

That is, each of Examples 9, 10, 12, 13, 15, 19, 20, 22, and 23 wasmixed with polyethylene, polypropylene, silicon resin, ABS, PS, acrylresin, natural rubber, or “HYBRAR” of Japanese Kuraray Co., LTD. andextruded or injected, and then blown to manufacture the specimens. TABLE4 Specimen Specimen Specimen Specimen Specimen Specimen SpecimenSpecimen Specimen Component 1 2 3 4 5 6 7 8 9 PE 95  2 30 — — — — — — PP 2 90 30 — — — — — — HDPE —  2 30  2 — — — — — LDPE —  1 — 25 — — — — —LLDPE — —  5 60 99 — — — — Silicon — — — 10 — 99 — — — ABS — — — — — —99 — — PC — — — — — — — 99 — PS — — — — — — — — 99 Antimicrobial Ex. 9Ex. 10 Ex. 12 Ex. 13 Ex. 15 Ex. 19 Ex. 20 Ex. 22 Ex. 23 Compound  3  5 5  3  1  1  1  1  1

The antimicrobial characteristics of the above specimens 1 to 9 weredetermined by ASTM G 22, which is the antimicrobial test method of theAmerican Society for Testing and Materials, and the yellowing wasdetermined according to ASTM D1925. The antimicrobial characters weretested against E. coli (KCTC 1682). TABLE 5 specimen Exp. Ex. specimen 1specimen 2 specimen 3 specimen 4 specimen 5 6-9 Anti-microbial grade 0grade 0 grade 0 grade 0 grade 0 grade 0 characteristics Yellowing passpass pass pass pass pass

The above Table 5 exhibits the results of the antimicrobialcharacteristics and yellowing tests of specimens 1 to 9, all of whichhad antimicrobial characteristics and did not cause yellowing.

EXPERIMENTAL EXAMPLE 2 Antimicrobial Test

The antimicrobial test was conducted by strain reduction ratedetermination (shake flask method). As the samples, 0.1 g of each of thecompounds of Examples 9, 13, 15, and 18 to 23 was used in the form ofpowder, and in the case of Examples 28 to 31, 2 ml of their stocksolution was used. The buffer solutions used in the antibacterial testwere those prepared by dissolving each of 28.39 g of NaHPO4 and 23.99 gof NaH2PO4 in 1000 ml of purified water, blending them in the volume of72 ml and 28 ml respectively, adding 5 g of NaCl thereto, and thenpouring purified water thereinto to adjust their total volume to 1000ml. As the control, the same bacterial strains, to which no samples wereadded, were used. The samples were mixed with bacterial strain inocula(5.0×105), which were then incubated while agitating for 24 hours andthen incubated on agar media. The reduction rate of strain number wasdetermined by the following Equation 1.(Reduction Rate %)={(A−B)/A}×100  [Equation 1]

-   -   A: Number of Bacteria in Control after 24 Hours

B: Number of Bacteria in Sample after 24 Hours TABLE 6 Strain RightAfter Reduction Sample Inoculation After 24 hours Rate (%) E. coliControl 4.81 × 10⁴  2.0 × 10⁷ — (KCTC 1682) Example 9 not detected notdetected 100 Example 13 not detected not detected 100 Example 15  1.5 ×10⁴ 1.99 99.99 Example 18  3.4 × 10⁵ 1.38 99.99 Example 19  4.8 × 10⁵2.22 × 10² 99.99 Example 20 5.37 × 10⁵ 1.7 99.99 Example 21 5.06 × 10⁵1.22 × 10² 99.99 Example 22 5.55 × 10⁵ 1.64 × 10² 99.99 Example 23 4.33× 10⁵ 1.35 × 10² 99.99 Example 28 4.37 × 10⁵ 1.92 99.99 Example 29 4.99× 10⁵ 3.44 × 10² 99.99 Example 30 2.53 × 10⁵ 1.18 99.99 Example 31 3.96× 10⁵ 2.09 × 10² 99.99 S. aureus Control 5.34 × 10⁴ 2.05 × 10⁷ — (KCTC1621) Example 9 not detected not detected 100 Example 13 not detectednot detected 100 Example 15 4.71 × 10⁴ 1.28 99.99 Example 18  5.6 × 10⁴1.14 99.99 Example 19 5.55 × 10⁵ 2.38 99.99 Example 20 4.11 × 10⁵ 6.2599.99 Example 21 5.88 × 10⁵ 1.38 × 10² 99.99 Example 22 3.62 × 10⁴ 1.01× 10² 99.99 Example 23 2.99 × 10⁴ 1.11 × 10² 99.99 Example 28 5.77 × 10⁶3.08 99.99 Example 29 5.96 × 10⁶ 1.34 × 10² 99.99 Example 30 4.21 × 10⁶2.15 99.99 Example 31 4.33 × 10⁶ 1.01 × 10² 99.99

In Table 6 above, “right after inoculation” refers to after 5 minutesfrom the time the bacterial strains were inoculated. The antimicrobialmonomer, antimicrobial acrylic copolymers, and antimicrobial polymericresins of the present invention exhibited excellent bactericidal abilityagainst E. coli and S.aureus. In addition, they exhibited goodantimicrobial activity against B. subtilis and M.luteus.

EXPERIMENTAL EXAMPLE 3 Light Stability Test of Antimicrobial AcrylicCopolymer

The antimicrobial monomers manufactured in Examples 9 and 10 and theantimicrobial acrylic copolymers manufactured in Examples 17 to 23 wereused as samples. 3 g of each sample were respectively put in lucid glasstest tubes, which were then placed under a direct ray of light. Also,according to the same method, the samples were collected in lucid glasstest tubes which were then sealed with aluminum foil and installed in aplace where indoor light was shut off. The changes in color wereobserved every two weeks for 3 months, and the results are shown inTable 7 below. TABLE 7 Two Four Six Eight Ten Twelve Weeks Weeks WeeksWeeks Weeks Weeks Initial Later Later Later Later Later Later DirectExample 9 white yellow orange light light brown brown Ray of brown brownLight Example white yellow orange light light brown brown 10 brown brownLight Example 9 white white white white white white white Shut Examplewhite white white white white white white Off 10 Direct Example whitewhite white white white white white Ray of 17 Light Example white whitewhite white white white white 18 Example light light light light lightlight light 19 yellow yellow yellow yellow yellow yellow yellow Examplelight light light light light light light 20 yellow yellow yellow yellowyellow yellow yellow Example light light light light light light light21 yellow yellow yellow yellow yellow yellow yellow Example yellowyellow yellow yellow yellow yellow yellow 22 Example yellow yellowyellow yellow yellow yellow yellow 23 Light Example white white whitewhite white white white Shut 17 Off Example white white white whitewhite white white 18 Example light light light light light light light19 yellow yellow yellow yellow yellow yellow yellow Example light lightlight light light light light 20 yellow yellow yellow yellow yellowyellow yellow Example light light light light light light light 21yellow yellow yellow yellow yellow yellow yellow Example yellow yellowyellow yellow yellow yellow yellow 22 Example yellow yellow yellowyellow yellow yellow yellow 23

From Table 7 above, it can be seen that the antimicrobial monomers ofExamples 9 and 10 were not discolored when installed in the place wherelight was shut off, and Examples 17 to 23 maintained stable color forthree months, and thus their light stability was excellent.

EXPERIMENTAL EXAMPLE 4 Skin Stimulation (Sensitivity) Test and HeatResistance Test

The antimicrobial acrylic copolymers manufactured in Examples 15, 20,and 22 were each added to polyethylene resin in an amount of 10% byweight, and master-batched. The produced master batch was added topolyethylene for film in an amount of 5% by weight, and blown tomanufacture a film. The film was cut into patches of 5 cm wide×5 cmlong, and 5 adult males and 5 adult females were subjected to a patchtest with them for 24 hours. The results are shown in Table 8 below, andit can be seen that no abnormal symptoms were observed in any of thesubjects of the test. TABLE 8 1 Hour 3 Hours 6 Hours 12 Hours 24 HoursGender Later Later Later Later Later Example Male x x x x x 15 Female xx x x x Example Male x x x x x 20 Female x x x x x Example Male x x x xx 22 Female x x x x xx: No Skin Stimulation∘: Skin Stimulation (Eruption, Red Spot, Tickling, Etc.)

Also, to investigate heat stability during the molding process, anantimicrobial test was conducted with regard to each film, and theresults are shown in Table 9. TABLE 9 Microbe Right After 24 HoursReduction Sample Innoculation⁵⁾ Later Rate(%) E. coli Control 5.44 × 10⁵2.38 × 10⁷ — (KCTC Polyethylene 1²⁾ 6.66 × 10⁵ 1.11 × 10² 99.99 1682)Polyethylene 2³⁾ 7.21 × 10⁵ 1.32 × 10² 99.99 Polyethylene 3⁴⁾ 5.18 × 10⁵2.16 × 10² 99.99 S. aureus Polyethylene 1²⁾ 7.77 × 10⁵ 1.88 × 10² 99.99(KCTC Polyethylene 2³⁾ 8.01 × 10⁵ 2.11 × 10² 99.99 1621) Polyethylene3⁴⁾ 6.55 × 10⁵ 1.99 × 10² 99.99 B. subtilis Polyethylene 1²⁾ 7.02 × 10⁵1.98 × 10² 99.99 (KCTC Polyethylene 2³⁾ 8.33 × 10⁵ 2.13 × 10² 99.991021) Polyethylene 3⁴⁾ 7.99 × 10⁵ 2.71 × 10² 99.99 M. luteusPolyethylene 1²⁾ 7.94 × 10⁵ 2.24 × 10² 99.99 (KCTC Polyethylene 2³⁾ 8.55× 10⁵ 2.75 × 10² 99.99 1071) Polyethylene 3⁴⁾ 8.68 × 10⁵ 1.99 × 10²99.99Notes)The amount of strains was 5.0 × 105 when initially inoculated.¹⁾Strain reduction rate determination²⁾Polyethylene film manufactured by Example 15³⁾Polyethylene film manufactured by Example 20⁴⁾Polyethylene film manufactured by Example 22⁵⁾Number of bacteria after 5 minutes from the time the strains wereinoculated

As shown in Table 9, it can be seen that the polyethylene filmsexhibited excellent antimicrobial effects even after the moldingprocess, and no sudden reduction in antimicrobial abilities due to heatdecomposition of antimicrobial substances was observed during themolding process into products.

EXPERIMENTAL EXAMPLE 5 Elution Test

4 g of each of the antimicrobial acrylic copolymers manufactured inExamples 20 and 22 above were added to 20 ml of 0.9% NaCl aqueoussolution, and after 24 hours at 70° C., they were cooled to roomtemperature and then filtered to prepare elution test solutions. Theantimicrobial effects of samples before and after tests and the elutiontest solution were determined and compared, and they are exhibited inTable 10 below. The solid samples were used in an amount of 20 μg,respectively, in the form of powder, and elution solutions weredetermined by dripping 20 μl of them on a paper disc. TABLE 10 E. coliS. aureus B. subtilis M. luteus (KCTC 1682) (KCTC 1621) (KCTC 1021)(KCTC 1071) Application Before 3.0 mm ± 0.5 mm 1.0 mm ± 0.5 mm 1.5 mm ±0.5 mm 2.5 mm ± 0.5 mm 1²⁾ Elution After 3.0 mm ± 0.5 mm 1.0 mm ± 0.5 mm1.5 mm ± 0.5 mm 2.5 mm ± 0.5 mm Elution Elution       0 mm       0 mm 0mm 0 mm Test Solution Application Before 2.5 ± 1 mm 0.5 ± 1 mm 1.0 mm ±0.5 mm 1.0 mm ± 0.5 mm 2³⁾ Elution After 2.5 ± 1 mm 0.5 ± 1 mm 1.0 mm ±0.5 mm 1.0 mm ± 0.5 mm Elution Elution       0 mm       0 mm 0 mm 0 mmTest Solution²⁾Antimicrobial acrylic copolymer of Example 20³⁾Antimicrobial acrylic copolymer of Example 22

From Table 10 above, it can be seen that all the samples both before andafter the elution test formed an inhibition zone having the same size,but in the elution test solutions, no inhibition zone was formed.

EXPERIMENTAL EXAMPLE 6 Oral Toxicity (Acute Toxicity) Test ofAntimicrobial Acrylic Copolymer

An oral toxicity test was conducted using the elution solution ofExample 20 above.

The test procedures followed No. 1999-61 of the Korea Food & DrugAdministration Notification. The test animals were Balb/C mice ofSamtaco, Co., and 5 each of five weeks-old male and female mice wereused. An oral administration route was used, the number ofadministrations was once, and a compulsory oral administration methodusing a sonde was employed. On the day the administration was carriedout, general conditions were observed every hour for 12 hours, and fromthe day after administration to 14 days, changes in general conditions,addiction symptoms, motion ability, appearance, and presence of deadanimals were observed once a day.

6-1. LD₅₀

As a result of the administration of 20 ml/kg B.W., which is theestablished maximum administrable amount, no dead animals were observed.Therefore, it was impossible to calculate a rough lethal dose.

6-2. Death Rate

During the whole period of the test, no deaths of the animals testedwere observed.

6-3. Clinic Symptom

Throughout the whole period of the test, no specific clinical symptomsappeared.

According to the above results, it can be seen that the antimicrobialacrylic copolymers were comparatively stable in respect of oraltoxicity.

EXAMPLE 32 Fabrication of Antimicrobial Master Batch for Medical Purposeand Antimicrobial Test

The antimicrobial monomers and antimicrobial polymeric compoundsmanufactured in Examples 9, 10, 15, and 22 above, and a dispersion agentLLDPE resin and an anti-oxidant agent, which are commercially ordinary,were each charged into a high-speed combining machine. They were thencombined by stirring them at a high speed for 30 minutes, followed byinjection-molding them in an injection molding machine at a moldingtemperature of 170˜190° C., to prepare the antimicrobial master batch inthe form of a pellet. Also, according to the same method, they wereapplied to HDPE and PP to thereby prepare the antimicrobial masterbatches, respectively. The ratios of each composition are as shown Table11 below. The antimicrobial test was performed by strain reduction ratedetermination (Shake flask method), and the results are shown in Table12. TABLE 11 Compositional Ratios of Antimicrobial Master Batch forMedical Purpose Dispersion Antimicrobial Agent/ Anti-Oxidant DispersionTotal Substance LLDPE¹⁾ HDPE²⁾ PP³⁾ Lubricant⁴⁾ Agent⁵⁾ Agent⁶⁾ (wt. %)Composition V Example 9 82.9 — — 2 0.1 10 100 (5%) Composition Example10 — 82.9 — 2 0.1 10 100 VI (5%) Composition Example 15 — — 83.4 1.5 0.110 100 VII (5%) Composition Example 22 82.9 — — 2 0.1 10 100 VIII (5%)Notes)¹⁾SK (Co.) Trademark CA 110;²⁾SK (Co.) Trademark JH 910;³⁾Trademark H360F;⁴⁾N,N′-ethylene bis steamide (E.B.S);⁵⁾n-octadecyl-3(3′-5′-di-t-butyl-4-hydroxyphenyl) propionate;⁶⁾Polyethylene Wax

TABLE 12 Antimicrobial Test Results of Antimicrobial Master Batch forMedical Purpose E. coli S. aureus (KCTC (KCTC S. typhimurium P.aeruginosa 1682) 1621) (KCTC 1925) (KCTC 2004) Composition V 99.99 99.9999.99 99.99 Composition 99.99 99.99 99.99 99.99 VI Composition 99.9999.99 99.99 99.99 VII Composition 99.99 99.99 99.99 99.99 VIII

EXAMPLE 33 Fabrication of Antimicrobial Catheter for Medical Purpose

The antimicrobial polymeric compounds produced by Examples 15 and 22were each added to medical grade silicon resin, with which catalysts,etc. were roll-combined with the compositional ratios shown in Table 13below for 30˜60 minutes and then processed by an injection moldingmachine to thereby fabricate an antimicrobial Foley catheter in the formof a tube. The molding process temperature was 450° C.˜600° C.×10seconds, and the product was cured for 2 hours by being maintained in adryer at 200° C. The antimicrobial effect was tested by strain reductionrate determination (Shake flask method), and the results are summarizedin Table 14. TABLE 13 Compositional Ratios of Antimicrobial SiliconFoley Catheter Antimicrobial Substance Peroxide Pt Example ExampleSilicon Catalyst Catalyst 15 22 Resin Total (wt. %) Composition I — 0.22.0 — 97.8 100 Composition 0.2 — — 2.0 97.8 100 II

TABLE 14 Antimicrobial Test Results of Antimicrobial Silicon FoleyCatheter S. aureus E. coli P. aeruginosa (AATC 1621) (AATC 1682) (AATC2004) Composition I 99.99 99.99 99.99 Composition II 99.99 99.99 99.99

EXAMPLE 34 Fabrication of Antimicrobial Polyurethane Artificial Legs forMedical Purpose

Medical grade polyurethane resins and the antimicrobial polymericcompounds obtained from Examples 15 and 22 were roll-combined for 2hours with the compositional ratios shown in Table 15 below, theninjected into a mold and vulcanized for 1 hour by being maintained at160° C., and then cooled to room temperature to thereby fabricateantimicrobial polyurethane artificial legs. The antimicrobialperformance was tested by the Shake flask method (Strain Reduction RateDetermination), and the determination results are shown in Table 16below. TABLE 15 Compositional Ratios of Antimicrobial PolyurethaneArtificial Legs Antimicrobial Material Polyurethane Category Example 15Example 22 Resin Total (wt. %) Composition 1.0 — 99.0 100 IIIComposition — 1.0 99.0 100 IV

TABLE 16 Antimicrobial Test Results of Antimicrobial PolyurethaneArtificial Legs S. aureus E. coli P. aeruginosa Strains Composition(AATC 1621) (AATC 1682) (AATC 2004) Composition III 99.99 99.99 99.99Composition IV 99.99 99.99 99.99

As mentioned above, the antimicrobial monomers and antimicrobialpolymeric compounds using them of the present invention have durableantimicrobial activity and high heat resistance, they do not give riseto toxicity when added to petrochemical materials such as conventionalpolymeric resins by not eluting the antimicrobial compounds, and they donot have an effect on the properties of molded products. Accordingly,the antimicrobial monomers of the present invention and theantimicrobial polymeric compounds using them can be easily and simplyapplied to industrial supplies such as various coatings, fibers,architectural materials, rubbers, medical supplies including medicaldevices for living bodies, and consumer supplies.

1-16. (canceled)
 17. The antimicrobial polymeric compound selected fromthe group consisting of compounds represented by the following formula 6to 9:

(in the formula 6 to 9, R′ is a group represented by the followingformula b:

wherein R is a saturated or unsaturated C₁ to C₁₅₀ hydrocarboncomprising a polymerizable functional group and a light-curable reactivefunctional group; R₁ and R₂ are each independently or simultaneouslyhydrogen, a halogen atom, an amine, or a C₁˜C₂₀ alkyl group; R₃ and R₄are each independently or simultaneously hydrogen, a hydroxy group, aC₁˜C₂₀ alkoxide, a halogen atom, or a C₁˜C₂₀ alkyl group; R₅ ishydrogen, a C₁˜C₂₀ alkyl, a cyclopropyl, or an aromatic C₁˜C₂₀hydrocarbon; R₆ is hydrogen, sodium, potassium, or a C₁˜C₁₅₀ alkyl groupthat comprises or does not comprise a polymerizable functional group;R₈, R₉, and R₁₀ are each independently or simultaneously carbon ornitrogen; and R₁, is hydrogen, an amine (1°, 2°, 3°), a halogen atom, ora C₁˜C₂₀ alkyl group.
 18. An antimicrobial acrylic copolymer having anaverage molecular weight of 10,000˜1,000,000, represented by thefollowing formula 10:

wherein R₁₂ and R₁₃ are each independently or simultaneously hydrogen ora methyl group; R₁₄ is a C₁˜C₁₈ alkyl group comprising one or moreselected from the group consisting of ester, carbonyl, amide, amine,cycloalkyl, ether, hydroxy, carboxylic acid, C_(2˜C) ₁₀ hetero ringcontaining N or O, sulfonyl, silane, lactone, and aldehyde groups; m andn are each an integer greater than zero satisfying said molecularweight; and X is a compound of the following formula 2a:

(wherein R₁˜R₆, and R₈˜R₁₁ are as defined in claim 17)
 19. A method ofmanufacturing the antimicrobial acrylic copolymer of formula 10 of claim18, comprising the step of radically polymerizing a compound of thefollowing formula 11:

wherein R₁₂ is hydrogen or a methyl group, and wherein X is a compoundof the following formula 2a

with a compound of the following formula 12:

wherein R₁₃ is hydrogen or a methyl group, and R₁₄ is a C₁˜C₁₈ alkylgroup comprising one or more selected from the group consisting ofester, carbonyl, amide, amine, cycloalkyl, ether, hydroxy, carboxylicacid, C_(2˜C) ₁₀ hetero ring containing N or O, sulfonyl, silane,lactone, and aldehyde groups.
 20. The method of the antimicrobialacrylic copolymer of claim 19, characterized in that said compound offormula 12 is an acrylic monomer consisting of a hydrocarbon main chainattributed to a vinyl alcohol, acrylonitrile, butadiene, acrylic acid,styrene, acrylimide, methylmethacrylic acid, methacrylic acid,vinylchloride, vinylfluoride, or vinylacetateacrylic acid as a mainchain.
 21. An antimicrobial polymeric resin composition in which a) apolymeric resin, and b) one of more antimicrobial compounds selectedfrom the group consisting of the antimicrobial polymeric compoundrepresented by the following formula 6 to 9, the acrylic copolymerrepresented by following formula 10, and the antimicrobial monomercompound represented by the following formula 11 are uniformly mixed.

(in the formula 6 to 9, R′ is a group represented by the followingformula b:

wherein R, R₁˜R₆, R₈˜R₁₁, R₁₂˜R₁₄, X, m and n are as defined in claim 17and claim 18).
 22. The antimicrobial polymeric resin composition ofclaim 21, which comprises said antimicrobial compound of b) in an amountof 0.1 to 30% by weight.
 23. The antimicrobial polymeric resincomposition of claim 21, wherein said composition further comprises c) apolyethylene wax in an amount of 0.1 to 10% by weight.
 24. Theantimicrobial polymeric resin composition of claim 21, characterized inthat said polymeric resin is one or more compounds selected from thegroup consisting of polyvinyl alcohol, polyacrylonitrile, polybutadiene,polyacrylic acid, polyacrylimide, polysulfone, polyacetal, polyimide,polytetrafluoroethylene, polyneophrene, polydimethylsiloxane,polymethylmethacrylate, polyetheretherketone, polyphenylenesulfide,polyvinylfluoride, polyvinylacetate, polyetherimide,polyvinyllidinefluoride, polyethersulfone, urethane resin, siliconresin, and natural rubber.
 25. The antimicrobial polymeric resincomposition of claim 21, characterized in that said antimicrobialpolymeric resin has a maximum release speed in water of 50 ppm/100 hrs.26. A light-curable resin composition comprising an acryliclight-curable oligomer, a property-fortified monomer, a light initiator,and an additive, wherein it comprises one or more antimicrobialcompounds selected from the group consisting of the antimicrobialpolymeric compound represented by the following formula 6 to 9, theacrylic copolymer represented by following formula 10, and theantimicrobial monomer compound represented by the following formula
 11.

(in the formula 6 to 9, R′ is a group represented by the followingformula b:

wherein R, R₁˜R₆, R₈˜R₁₁, R₁₂˜R₁₄, X, m and n are as defined in theformula claim 17 and claim 18).
 27. The light-curable resin compositionof claim 26 which comprises said antimicrobial compounds in an amount of0.1 to 30% by weight.
 28. A molded or processed product comprising thepolymeric resin composition of claim
 21. 29. The molded and processedproduct of claim 28, wherein said molded and processed product is apetrochemical product characterized by industrial supplies, consumersupplies, or medical supplies.
 30. The molded and processed product ofclaim 28, wherein said molded and processed product is an antimicrobialpolymeric resin product characterized by blinds; wall paper; floorcoverings; food-related products including films for wrapping, storagecontainers, and cutting boards; water purifiers; humidifiers; washers;dish washers; refrigerators; appliances; water supply and drain pipes;concrete; engineering materials and coatings; fibers; catheters formedical purposes; microbionic chip materials; ventilating tubes foreardrums; nursing bottles; prostheses; products for fixing bones; orblood transfusion bags for medical purposes. 31-34. (canceled)
 35. Theantimicrobial polymeric resin composition according to claim 21, whereinsaid the antimicrobial polymeric compound represented by the followingformula 6 to 9 is obtained by the steps of binding the antimicrobialmonomer described in claim 21 to a linker selected from the groupconsisting of an isocyanate class, a haloacylhalogenade, and a compoundcontaining an acid anhydride, in the presence of an organic solvent, andthen reacting it with a polyol. 36-39. (canceled)
 40. The antimicrobialpolymeric resin composition according to claim 26, wherein said theantimicrobial polymeric compound represented by the following formula 6to 9 is obtained by the steps of binding the antimicrobial monomerdescribed in claim 26 to a linker selected from the group consisting ofan isocyanate class, a haloacylhalogenade, and a compound containing anacid anhydride, in the presence of an organic solvent, and then reactingit with a polyol.
 41. A compound represented by following formula 11:

wherein R₁₂ is hydrogen or a methyl group, and X is a compound of thefollowing formula 2a

wherein R₁ and R₂ are each independently or simultaneously hydrogen, ahalogen atom, an amine, or a C₁˜C₂₀ alkyl group; R₃ and R₄ are eachindependently or simultaneously hydrogen, a hydroxy group, a C₁˜C₂₀alkoxide, a halogen atom, or a C₁˜C₂₀ alkyl group; R₅ is hydrogen, aC₁˜C₂₀ alkyl, a cyclopropyl, or an aromatic C₁˜C₂₀ hydrocarbon; R₆ ishydrogen, sodium, potassium, or a C₁˜C₁₅₀ alkyl group that comprises ordoes not comprise a polymerizable functional group; R₈, R₉, and R₁₀ areeach independently or simultaneously carbon or nitrogen; and R₁₁ ishydrogen, an amine (10, 20, 3°), a halogen atom, or a C₁˜C₂₀ alkylgroup.
 42. A method for preparing compound of formula 11 of claim 41comprising the step of an epoxide ring-opening reaction of the compoundrepresented by formula 2 with an epoxide compound having a double bond.

(wherein R₁˜R₆ and R₈˜R₁₁ are as defined in formula 1 described in claim21)
 43. The method for preparing compound of formula 11 according toclaim 42, wherein said epoxide compound having a double bond isglycidylmethacrylate.
 44. A molded or processed product comprising thepolymeric resin composition of claim 26.